CN109096754A - A kind of MXene- poly-dopamine composite material and preparation method - Google Patents

A kind of MXene- poly-dopamine composite material and preparation method Download PDF

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CN109096754A
CN109096754A CN201810762327.0A CN201810762327A CN109096754A CN 109096754 A CN109096754 A CN 109096754A CN 201810762327 A CN201810762327 A CN 201810762327A CN 109096754 A CN109096754 A CN 109096754A
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mxene
nanometer sheet
poly
dopamine
compound
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凌铮
宋永臣
王博浩
张晓东
石常瑞
李峰
陈乾
刘冬蕾
赵佳飞
杨磊
李洋辉
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Dalian University of Technology
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

A kind of MXene- poly-dopamine composite material and preparation method, composite materials are that two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet being release-treated and the poly-dopamine for being wrapped in the MXene nanometer sheet surface are constituted；Wherein, the mass ratio of two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet and poly-dopamine is 1:0.05~1:1.The present invention improves the stability of MXene nanometer sheet by the way that poly-dopamine to be wrapped in the surface for two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet that lift-off processing obtains using the reduction and package action of poly-dopamine；The interlamellar spacing of MXene nanometer sheet is increased using the supporting role of poly-dopamine simultaneously, has obtained the MXene- poly-dopamine composite material with high stability and excellent ion and gas storage characteristics；And preparation step of the invention is simple, is suitable for large-scale production.

Description

A kind of MXene- poly-dopamine composite material and preparation method
Technical field
The invention belongs to new material and field of energy environment, especially a kind of MXene- poly-dopamine composite material and its system Preparation Method.
Background technique
MXene is a kind of novel two-dimentional transition metal carbides or nitride, big by U.S. Drexel in 2011 Researcher reports for the first time.MXene material family member is abundant, and the chemical general formula of the material is Mn+1XnTx, wherein M is transition Metallic element, X are carbon or nitrogen, and the integer that n is 1~3, T is surface functional group, and x is the quantity of functional group.MXene is same When conductive and water-wet behavior, therefore ion storage, energy convert etc. many fields have fabulous application prospect.So And since the surface MXene has the metallic atom of exposure, it is easily oxidized, so that structure and electric conductivity are destroyed；Furthermore The interlamellar spacing for the MXene film that MXene and the MXene nanometer sheet by removing are constituted is smaller, absorption and biography for ion, gas It is defeated to cause to hinder.
Summary of the invention
The object of the present invention is to provide one kind can effectively avoid the oxidation of MXene material surface, facilitates MXene nanoscale twins The increase of spacing, improve ion and molecule the simple MXene- poly-dopamine composite material of storage characteristics and preparation step and its Preparation method.
The present invention solves a kind of technical solution used by prior art problem: MXene- poly-dopamine composite material, should Composite materials are two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheets being release-treated and are wrapped in the two dimension The poly-dopamine on magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet surface is constituted；Wherein, two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) is changed The mass ratio of object MXene nanometer sheet and poly-dopamine is 1:0.05~1:1.
The structural formula of described two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is Ti3C2Tx,Ti2CTx,Nb2CTx, Wherein T is the functional group on the surface multilayer MXene, and x is the quantity of functional group.
Two dimension magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet is few layer or single layer MXene nanometer sheet.
A kind of preparation method of MXene- poly-dopamine composite material, comprising the following steps:
S1, selective corrosion raw material MAX powder obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet:
Corrode raw material MAX powder under default corrosion temperature using hydrofluoric acid or generated in-situ hydrofluoric acid, and gone from Multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is obtained after sub- water washing, drying；Hydrofluoric acid and raw material MAX powder The ratio at end is that 10mL hydrofluoric acid is added in every gram of raw material MAX powder；
S2, removing multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet obtain few layer and MXene nanometers of single layer Piece dispersion liquid:
Multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is dispersed in water, it is sharp under protective atmosphere Lift-off processing is carried out with ultrasound or mechanical stirring, obtains few layer and single layer MXene nanometer sheet dispersion liquid by centrifugal treating；
S3, the pH value for adjusting few layer and single layer MXene nanometer sheet dispersion liquid, few layer and single layer MXene nanometer sheet are dispersed Liquid is reacted with Dopamine hydrochloride mixing:
After the pH value of the obtained few layer of step S2 and single layer MXene nanometer sheet dispersion liquid is adjusted to 8~10, at room temperature Few layer after pH value will be adjusted and single layer MXene nanometer sheet dispersion liquid and Dopamine hydrochloride is stirred mixing and reacts the two, Reaction time is for 24 hours, to obtain MXene- poly-dopamine compound dispersion liquid；Wherein, when being stirred, few layer and single layer are controlled The mass ratio of few layer and single layer MXene nanometer sheet and Dopamine hydrochloride in MXene nanometer sheet dispersion liquid is 1:0.05~1:1；
S4, MXene- poly-dopamine compound dispersion liquid is filtered to obtain MXene- poly-dopamine composite materials:
The MXene- poly-dopamine compound dispersion liquid that step S3 is obtained is filtered by vacuum, is washed with deionized, is passed through MXene- poly-dopamine composite materials are obtained after drying.
The ingredient of the raw material MAX are as follows: Ti3AlC2,Ti2AlC、Nb2AlC；Through the obtained multilayer two-dimension transition of step S1 The structural formula of race metal carbon (nitrogen) compound MXene nanometer sheet is Ti3C2Tx,Ti2CTx,Nb2CTx, wherein T is the surface multilayer MXene Functional group, x be functional group quantity.
The partial size of the raw material MAX powder is at 38 μm hereinafter, the concentration of hydrofluoric acid is in 6~12mol/L, preset corrosion temperature Degree is at 25~55 DEG C.
In step S2, in centrifugal treating, the centrifuge RPMs of centrifugal device are adjusted at 2000~10000 revs/min.
In step S2, the time of lift-off processing is 10-120min；In step S3, few layer and the dispersion of single layer MXene nanometer sheet The pH value of liquid is adjusted by organic base and inorganic base.
The protective atmosphere is nitrogen or argon gas.
Reduction and package action the beneficial effects of the present invention are: the present invention using poly-dopamine, by by poly- DOPA Amine is wrapped in the surface for two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet that lift-off processing obtains, and avoids MXene and receives Rice piece oxidation, improves the stability of MXene nanometer sheet；MXene nanometers are increased using the supporting role of poly-dopamine simultaneously Piece interlamellar spacing has obtained the MXene- poly-dopamine composite wood with high stability and excellent ion and gas storage characteristics Material；And preparation step of the invention is simple, is suitable for large-scale production.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described:
A kind of MXene- poly-dopamine composite material, the composite materials are the two-dimentional transition group gold being release-treated Belong to carbon (nitrogen) compound MXene nanometer sheet and is wrapped in the poly- of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet surface Dopamine is constituted；Wherein, two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet being release-treated be few layer or Single layer MXene nanometer sheet.The mass ratio of two dimension magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet and poly-dopamine is 1: 0.05~1:1.Specifically, the structural formula of two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is Ti3C2Tx,Ti2CTx, Nb2CTx, wherein T is the functional group on the surface multilayer MXene, and x is the quantity of functional group.
A kind of preparation method of MXene- poly-dopamine composite material of the present invention is illustrated by following specific embodiments:
Embodiment 1:
A kind of preparation method of MXene- poly-dopamine composite material, comprising the following steps:
S1, selective corrosion ingredient are Ti3AlC2MAX powder obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti3C2TxNanometer sheet:
It is Ti that ingredient of the partial size less than 38 μm is added into hydrofluoric acid3AlC2MAX powder (referred to as Ti3AlC2Powder), Hydrofluoric acid concentration is 12mol/L, hydrofluoric acid and Ti3AlC2The ratio of powder is every gram of Ti3AlC210mL hydrofluoric acid is added in powder. By hydrofluoric acid and Ti3AlC2The mixture of powder under default corrosion temperature 25 DEG C stirring for 24 hours, be then washed with deionized, It is dry, obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti3C2TxNanometer sheet.Wherein T is the function on the surface multilayer MXene Group, x are the quantity nanometer sheet of functional group.
S2, removing multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti3C2TxNanometer sheet obtains few layer and single layer Ti3C2Tx Nanometer sheet dispersion liquid:
By multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti3C2TxNanometer sheet is dispersed in water, under nitrogen protection, benefit Lift-off processing is carried out with mechanical stirring, is then in 10000 revs/min of centrifugal device to being dispersed in water in centrifugal rotational speed Ti3C2TxNanometer sheet carries out centrifugal treating and obtains few layer and single layer Ti3C2TxNanometer sheet dispersion liquid.
S3, few layer and single layer Ti are adjusted3C2TxThe pH value of nanometer sheet dispersion liquid, by few layer and single layer Ti3C2TxNanometer sheet point Dispersion liquid is reacted with Dopamine hydrochloride mixing:
Using inorganic bases such as sodium hydroxide, potassium hydroxide by the obtained few layer of step S2 and single layer Ti3C2TxNanometer sheet dispersion After the pH value of liquid is adjusted to 8, the few layer and single layer Ti that are at room temperature 8 by pH value3C2TxNanometer sheet dispersion liquid and Dopamine hydrochloride Carrying out mechanical stirring mixing makes the two reaction for 24 hours, obtains Ti3C2TxPoly-dopamine compound dispersion liquid；Wherein, machinery is being carried out When being stirred, few layer and single layer Ti are controlled3C2TxFew layer and single layer Ti in nanometer sheet dispersion liquid3C2TxNanometer sheet and hydrochloric acid are more The mass ratio of bar amine is 1:0.05.
S4, to Ti3C2TxPoly-dopamine compound dispersion liquid is filtered, and Ti is obtained3C2TxPoly-dopamine compound material Material:
The Ti that step S3 is obtained3C2TxPoly-dopamine compound dispersion liquid is filtered by vacuum, and is washed with deionized 3 It is secondary, Ti is obtained after drying3C2TxPoly-dopamine composite materials.
Through analysis detection and calculate discovery Ti3C2TxThe interlamellar spacing of poly-dopamine is 2.8nm, greater than original Ti3C2TxIt receives Rice piece interlamellar spacing, and the material is placed 6 months and does not occur problem of oxidation.Be used as supercapacitor carry out ion storage, three Under electrode system, volumetric capacitance is up to 310F/cm in sulfuric acid electrolyte3。
Embodiment 2:
A kind of preparation method of MXene- poly-dopamine composite material, comprising the following steps:
S1, selective corrosion ingredient are Nb2The MAX powder of AlC obtains multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Nb2CTxNanometer sheet:
It is Nb that ingredient of the partial size less than 38 μm is added into hydrofluoric acid2MAX powder (the referred to as Nb of AlC2AlC powder), hydrogen Fluoric acid concentration is 9mol/L, hydrofluoric acid and Nb2The ratio of AlC powder is every gram of Nb210mL hydrofluoric acid is added in AlC powder.By hydrogen fluorine Acid and Nb2The mixture of AlC powder under default corrosion temperature 35 DEG C stirring for 24 hours, be then washed with deionized, it is dry, Obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Nb2CTxNanometer sheet.Wherein T is the functional group on the surface multilayer MXene, and x is The quantity nanometer sheet of functional group.
S2, removing multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Nb2CTxNanometer sheet obtains few layer and single layer Nb2CTxIt receives Rice piece dispersion liquid:
By multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Nb2CTxNanometer sheet is dispersed in water, and under protection of argon gas, is utilized Ultrasonic agitation carries out lift-off processing, then to the Nb being dispersed in water in the centrifugal device that centrifugal rotational speed is 4500 revs/min2CTx Nanometer sheet carries out centrifugal treating, obtains few layer and single layer Nb2CTxNanometer sheet dispersion liquid.
S3, few layer and single layer Nb are adjusted2CTxThe pH value of nanometer sheet dispersion liquid, by few layer and single layer Nb2CTxNanometer sheet dispersion Liquid is reacted with Dopamine hydrochloride mixing:
Using inorganic bases such as sodium hydroxide, potassium hydroxide by the obtained few layer of step S2 and single layer Nb2CTxNanometer sheet dispersion After the pH value of liquid is adjusted to 9, the few layer and single layer Nb that are at room temperature 9 by pH value2CTxNanometer sheet dispersion liquid and Dopamine hydrochloride Carrying out mechanical stirring mixing makes the two reaction for 24 hours, obtains Nb2CTxPoly-dopamine compound dispersion liquid；Wherein, machinery is being carried out When being stirred, few layer and single layer Nb are controlled2CTxFew layer and single layer Nb in nanometer sheet dispersion liquid2CTxNanometer sheet and hydrochloric acid are more The mass ratio of bar amine is 1:0.5.
S4, to Nb2CTxPoly-dopamine compound dispersion liquid is filtered, and Nb is obtained2CTxPoly-dopamine compound material Material:
The Nb that step S3 is obtained2CTxPoly-dopamine compound dispersion liquid is filtered by vacuum, and is washed with deionized 3 times, Nb is obtained after drying2CTxPoly-dopamine composite materials.
Through analysis detection and calculate discovery, Nb2CTxThe interlamellar spacing of poly-dopamine is 2.8nm, greater than original Nb2CTxIt receives Rice piece interlamellar spacing, and the material is placed 6 months and does not occur problem of oxidation.
Embodiment 3:
A kind of preparation method of MXene- poly-dopamine composite material, comprising the following steps:
S1, selective corrosion ingredient are Ti2The MAX powder of AlC obtains multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti2CTxNanometer sheet:
Ti of the partial size less than 38 μm is added in the hydrofluoric acid in situ formed to hydrochloric acid and lithium fluoride2MAX powder (the letter of AlC Referred to as Ti2AlC powder), hydrofluoric acid concentration 6mol/L, hydrofluoric acid and Ti2The ratio of AlC powder is every gram of Ti2AlC powder adds Enter 10mL hydrofluoric acid.By hydrofluoric acid in situ and Ti2The mixture of AlC powder under default corrosion temperature 55 DEG C stirring for 24 hours, so After be washed with deionized, it is dry, obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti2CTxNanometer sheet.Wherein T is multilayer The functional group on the surface MXene, x are the quantity nanometer sheet of functional group.
S2, removing multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti2CTxNanometer sheet obtains few layer and single layer Ti2CTxIt receives Rice piece dispersion liquid:
By multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound Ti2CTxNanometer sheet is dispersed in water, and under nitrogen protection, is utilized Ultrasonic agitation carries out lift-off processing, then to the Ti being dispersed in water in the centrifugal device that centrifugal rotational speed is 2000 revs/min2CTx Nanometer sheet carries out centrifugal treating, obtains few layer and single layer Ti2CTxNanometer sheet dispersion liquid.
S3, few layer and single layer Ti are adjusted2CTxThe pH value of nanometer sheet dispersion liquid, by few layer and single layer Ti2CTxNanometer sheet dispersion Liquid is reacted with Dopamine hydrochloride mixing:
Using inorganic bases such as sodium hydroxide, potassium hydroxide by the obtained few layer of step S2 and single layer Ti2CTxNanometer sheet dispersion After the pH value of liquid is adjusted to 10, the few layer and single layer Ti that are at room temperature 10 by pH value2CTxNanometer sheet dispersion liquid and hydrochloric acid DOPA Amine, which carries out mechanical stirring mixing, makes the two reaction for 24 hours, obtains Ti2CTxPoly-dopamine compound dispersion liquid；Wherein, in the machine of progress When tool stirs, few layer and single layer Ti are controlled2CTxFew layer and single layer Ti in nanometer sheet dispersion liquid2CTxNanometer sheet and hydrochloric acid DOPA The mass ratio of amine is 1:1.
S4, to Ti2CTxPoly-dopamine compound dispersion liquid is filtered, and Ti is obtained2CTxPoly-dopamine compound material Material:
The Ti that step S3 is obtained2CTxPoly-dopamine compound dispersion liquid is filtered by vacuum, and is washed with deionized 4 times, Ti is obtained after drying2CTxPoly-dopamine composite materials.
Through analysis detection and calculate discovery, Ti2CTxThe interlamellar spacing of poly-dopamine is 4.2nm, greater than original Ti2CTxIt receives Rice piece interlamellar spacing, and the material is placed 6 months and does not occur problem of oxidation.It is excellent that material surface amino abundant has material Different CO2Absorption property.
The above content is combine specific optimal technical scheme further detailed description of the invention, and it cannot be said that Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention Protection scope.

Claims (9)

1. a kind of MXene- poly-dopamine composite material, which is characterized in that the composite materials are two be release-treated It ties up magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet and is wrapped in MXene nanometers of (nitrogen) compound of the two dimension magnesium-yttrium-transition metal carbon The poly-dopamine on piece surface is constituted；Wherein, the quality of two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet and poly-dopamine Than for 1:0.05~1:1.
2. a kind of MXene- poly-dopamine composite material according to claim 1, which is characterized in that the two dimension transition group The structural formula of metal carbon (nitrogen) compound MXene nanometer sheet is Ti3C2Tx,Ti2CTx,Nb2CTx, wherein T is the surface multilayer MXene Functional group, x are the quantity of functional group.
3. a kind of MXene- poly-dopamine composite material according to claim 1, which is characterized in that the two dimension transition group Metal carbon (nitrogen) compound MXene nanometer sheet is few layer or single layer MXene nanometer sheet.
4. a kind of preparation method of MXene- poly-dopamine composite material according to claim 1, which is characterized in that including Following steps:
S1, selective corrosion raw material MAX powder obtain multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet:
Corrode raw material MAX powder under default corrosion temperature using hydrofluoric acid or generated in-situ hydrofluoric acid, and through deionized water Multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is obtained after washing, drying；Hydrofluoric acid and raw material MAX powder Ratio is that 10mL hydrofluoric acid is added in every gram of raw material MAX powder；
S2, removing multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet obtain few layer and single layer MXene nanometer sheet point Dispersion liquid:
Multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet is dispersed in water, using super under protective atmosphere Sound or mechanical stirring carry out lift-off processing, obtain few layer and single layer MXene nanometer sheet dispersion liquid by centrifugal treating；
S3, the pH value for adjusting few layer and single layer MXene nanometer sheet dispersion liquid, by few layer and single layer MXene nanometer sheet dispersion liquid with Dopamine hydrochloride mixing is reacted:
After the pH value of the obtained few layer of step S2 and single layer MXene nanometer sheet dispersion liquid is adjusted to 8~10, it will adjust at room temperature Few layer and single layer MXene nanometer sheet dispersion liquid after section pH value, which are stirred mixing with Dopamine hydrochloride, reacts the two, reacts Time is for 24 hours, to obtain MXene- poly-dopamine compound dispersion liquid；Wherein, when being stirred, few layer and single layer are controlled The mass ratio of few layer and single layer MXene nanometer sheet and Dopamine hydrochloride in MXene nanometer sheet dispersion liquid is 1:0.05~1:1；
S4, MXene- poly-dopamine compound dispersion liquid is filtered to obtain MXene- poly-dopamine composite materials:
The MXene- poly-dopamine compound dispersion liquid that step S3 is obtained is filtered by vacuum, is washed with deionized, through drying After obtain MXene- poly-dopamine composite materials.
5. a kind of preparation method of MXene- poly-dopamine composite material according to claim 4, which is characterized in that described The ingredient of raw material MAX are as follows: Ti3AlC2,Ti2AlC、Nb2AlC；Through the obtained multilayer two-dimension magnesium-yttrium-transition metal carbon (nitrogen) of step S1 The structural formula of compound MXene nanometer sheet is Ti3C2Tx,Ti2CTx,Nb2CTx, wherein T is the functional group on the surface multilayer MXene, and x is The quantity of functional group.
6. a kind of MXene- poly-dopamine composite material and preparation method according to claim 4, which is characterized in that institute The partial size of raw material MAX powder is stated at 38 μm hereinafter, the concentration of hydrofluoric acid is in 6~12mol/L, preset corrosion temperature is 25~55 ℃。
7. a kind of MXene- poly-dopamine composite material and preparation method according to claim 4, which is characterized in that step In rapid S2, in centrifugal treating, the centrifuge RPMs of centrifugal device are adjusted at 2000~10000 revs/min.
8. a kind of MXene- poly-dopamine composite material and preparation method according to claim 4, which is characterized in that step In rapid S2, the time of lift-off processing is 10-120min；In step S3, the pH value of few layer and single layer MXene nanometer sheet dispersion liquid is logical It crosses organic base and inorganic base is adjusted.
9. a kind of MXene- poly-dopamine composite material and preparation method according to claim 4, which is characterized in that institute Stating protective atmosphere is nitrogen or argon gas.
CN201810762327.0A 2018-07-12 2018-07-12 A kind of MXene- poly-dopamine composite material and preparation method Pending CN109096754A (en)

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